Nonvolatile semiconductor memory device and method of manufacturing the same

ABSTRACT

A nonvolatile semiconductor memory device includes a floating gate electrode which is selectively formed on a main surface of a first conductivity type with a first gate insulating film interposed therebetween, a control gate electrode formed on the floating gate electrode with a second gate insulating film interposed therebetween, and source/drain regions of a second conductivity type which are formed in the main surface of the substrate in correspondence with the respective gate electrodes. The first gate electrode has a three-layer structure in which a silicon nitride film is held between silicon oxide films, and the silicon nitride film includes triple coordinate nitrogen bonds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. non-provisional applicationSer. No. 11/083,035, filed Mar. 18, 2005, to which the benefit ofpriority under 35 U.S.C. 120 is claimed. This application is also basedupon and claims the benefit of priority from prior Japanese PatentApplication No. 2004-185497, filed Jun. 23, 2004, and the entirecontents of both applications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a nonvolatile semiconductor memory devicehaving a stacked gate structure formed by stacking a floating gateelectrode and a control gate electrode on a semiconductor substrate, anda method of manufacturing the same. In particular, this inventionrelates to a nonvolatile semiconductor memory device and a method ofmanufacturing the same for improving a tunnel insulating film between afloating gate electrode and a substrate.

2. Description of the Related Art

Recently, in electrically programmable and erasable nonvolatilesemiconductor memory devices (EEPROM), scale down of the devices hasbeen being rapidly promoted. In EEPROMs, there has been adopted a methodin which electrons are injected into a floating gate electrode from asubstrate through a tunnel oxide film (writing), or electrons in thefloating gate electrode are extracted therefrom (erase), by applying ahigh voltage to a control gate electrode.

In this operation, a high voltage is required to inject or extractelectrons into (from) the floating gate electrode, and a large stress isapplied to the tunnel oxide film. Thereby, a defect called “trap” isgenerated in the tunnel oxide film, a leak current increases, and dataholding property and the like are hindered. A leak current caused bystress application strongly depends on the film thickness of the tunneloxide film. The thinner the tunnel oxide film is, the more likely theleak current flows. This phenomenon is a large factor which hindersreduction in the thickness of the tunnel oxide film.

As means for solving the problem, adopted is a method in which nitrogenis introduced into the tunnel oxide film, thereby a dielectric constantthereof as the tunnel insulating film is increased and physical filmthickness of the film is increased to reduce the leak current. In thismethod, nitrogen introduced into the tunnel insulating film, byannealing a silicon oxide film by ammonia (NH₃) gas, carbon monoxide(NO) gas, or dinitrogen monoxide (N₂O). However, in treatment using NH₃gas or the like, a large amount of hydrogen is introduced into thetunnel insulating film, and an after heat treatment at high temperatureis required to secure the reliability of the device. Further, treatmentusing NO or N₂O has a problem, such as increase in the hole trap amountin stress application, which deteriorates the reliability (Jpn. Pat.Appln. KOKAI Pub. No. 1-307272).

In the meantime, to increase the coupling ratio between the control gateelectrode and the floating gate electrode, it has been proposed to usean insulating film having a dielectric constant higher than that of theconventional silicon oxide film and silicon oxynitride film as aninterelectrode insulating film. However, if a high-dielectric-constantinsulating film, such as a metal oxide, is used as an interelectrodeinsulating film, the metal diffuses into the tunnel insulating filmthrough the floating gate electrode, and greatly deteriorates thereliability of the device.

As described above, as the tunnel insulating film of EEPROMs, requiredis an insulating film which does not easily form traps due tohigh-voltage stress application and has a reduced leak current. However,in prior art, it is very difficult to meet such specs. Further, using ahigh-dielectric-constant insulating film such as a metal oxide theinterelectrode insulating film causes the problem that the metal isdiffused through the floating gate electrode into the tunnel insulatingfilm and causes deterioration in the reliability of the tunnelinsulating film.

BRIEF SUMMARY OF THE INVENTION

According to an aspect of the present invention, a nonvolatilesemiconductor memory device comprises: a semiconductor substrate of afirst conductivity type; a gate element formed on the semiconductorsubstrate, and comprising: a first gate insulating film which isselectively formed on a main surface of the semiconductor substrate, thefirst gate insulating film forming a three-layer structure including asilicon nitride film and silicon oxide films between which the siliconnitride film is sandwiched, the silicon nitride film including triplecoordinate nitrogen bonds; a floating gate electrode formed on the firstgate insulating film; a second gate insulating film formed on thefloating gate electrode; and a control gate electrode formed on thesecond gate insulating film; and source and drain regions of a secondconductivity type, the source and drain regions being formed in the mainsurface of the substrate with the gate element being arranged betweenthe source and drain regions.

According to another aspect of the present invention, a method ofmanufacturing a nonvolatile semiconductor memory device, comprises:forming a silicon nitride film by directly nitriding a main surface of asilicon substrate of a first conductivity type, followed by heating thesubstrate in an oxidizing atmosphere, to form silicon oxide films, onein an interface between the silicon nitride film and the substrate andthe other on the silicon nitride film, the silicon oxide films and thesilicon nitride film and forming a first gate insulating film; forming afloating gate electrode on the first gate insulating film; forming asecond gate insulating film on the floating gate electrode; forming acontrol gate electrode on the second gate insulating film; and formingsource and drain regions of a second conductivity type in the mainsurface of the substrate with the first gate insulating film beingarranged between the source and drain regions.

According to another aspect of the present invention, a method ofmanufacturing a nonvolatile semiconductor memory device, comprises:forming a silicon nitride film by directly nitriding a main surface of asilicon substrate of a first conductivity type, followed by forming asilicon film on the silicon nitride film, followed by heating thesubstrate in an oxidizing atmosphere to oxidize the silicon film andform a first silicon oxide film, and forming a second silicon oxide filmin an interface between the silicon nitride film and the substrate, thesilicon nitride film, the first silicon oxide film and the secondsilicon oxide film forming a first gate insulating film; forming afloating gate electrode on the first gate insulating film; forming asecond gate insulating film on the floating gate electrode; forming acontrol gate electrode on the second gate insulating film; and formingsource and drain regions of a second conductivity type in the mainsurface of the substrate with the first gate insulating film beingarranged between the source and drain regions.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIG. 1 is a cross-sectional view illustrating a schematic structure of anonvolatile semiconductor memory device according to a first embodimentof the present invention.

FIGS. 2A and 2B are diagrams illustrating equivalent circuits of thenonvolatile semiconductor memory device of FIG. 1 and a NAND cell unitusing the same.

FIG. 3 is a cross-sectional view illustrating a structure of a tunnelinsulating film used in the first embodiment.

FIG. 4 is a schematic diagram for explaining the effect of the firstembodiment, illustrating a bond state of nitrogen.

FIGS. 5A to 5C are schematic diagrams for explaining the effect of thefirst embodiment, illustrating steps for forming a silicon nitride filmand a bond state of nitrogen in prior art.

FIG. 6 is a characteristic diagram for explaining the effect of thefirst embodiment, illustrating a comparison between stress inductionleak currents in tunnel insulating films according to prior art and thefirst embodiment.

FIGS. 7A to 7D are cross-sectional views illustrating steps ofmanufacturing a nonvolatile semiconductor memory device according to asecond embodiment.

FIG. 8 is a characteristic diagram for explaining the effect of thesecond embodiment, illustrating relationship between a processtemperature and a roughness state (surface roughness) of the surface ofa silicon nitride film.

FIG. 9 is a characteristic diagram for explaining the effect of thesecond embodiment, illustrating a silicon nitride film formingtemperature and a bond state.

FIG. 10 is a schematic diagram for explaining the effect of the secondembodiment, illustrating the relationship between the temperature andpressure in formation of the silicon nitride film and film quality ofthe silicon nitride film.

FIG. 11 is a characteristic diagram for explaining the effect of thesecond embodiment, illustrating oxygen density distribution in a tunnelinsulating film.

FIG. 12 is a characteristic diagram for explaining the effect of thesecond embodiment, illustrating the relationship between a voltageapplied to the tunnel insulating film and the capacity.

FIGS. 13A to 13I are cross-sectional views illustrating manufacturingsteps of a nonvolatile semiconductor memory device according to a thirdembodiment of the present invention.

FIGS. 14A to 14D are cross-sectional views illustrating manufacturingsteps of a nonvolatile semiconductor memory device according to a fourthembodiment of the present invention.

FIG. 15 is a cross-sectional view for explaining the effect of thefourth embodiment, illustrating a specific structure of a tunnelinsulating film.

FIG. 16 is a cross-sectional view illustrating a schematic structure ofa nonvolatile semiconductor memory device according to a fifthembodiment of the present invention.

FIGS. 17A to 17D are cross-sectional views illustrating manufacturingsteps of a nonvolatile semiconductor memory device according to a sixthembodiment.

FIGS. 18A to 18E are cross-sectional views illustrating manufacturingsteps of a nonvolatile semiconductor memory device according to aseventh embodiment.

FIG. 19 is a cross-sectional view for explaining a modification of thenonvolatile semiconductor memory device according to the seventhembodiment, illustrating an example of a semiconductor memory deviceusing the particle effect.

DETAILED DESCRIPTION OF THE INVENTION

Details of the present invention will be explained with reference toembodiments shown in drawings.

First Embodiment

FIG. 1 is a cross-sectional view illustrating a schematic structure of anonvolatile semiconductor memory device according to a first embodimentof the present invention.

Silicon oxide films 12 for device isolation are embedded in a p-type(first conductivity type) silicon substrate 11, to surround a deviceregion in a main surface of the silicon substrate 11. On the mainsurface of the silicon substrate 11, a floating gate electrode 14 isformed with a tunnel insulating film (first gate insulating film) 13interposed therebetween. A control gate electrode 16 is formed on thefloating gate electrode 14 with an interelectrode insulating film(second gate insulating film) 15 interposed therebetween. Theinterelectrode insulating film 15 is an ONO film formed of a siliconoxide film, a CVD silicon nitride film, and a CVD silicon oxide film andhaving a 7 nm thickness. Each of the floating gate electrode 14 and thecontrol gate electrode 16 is formed of a polycrystalline silicon film.

A silicon oxide film 17 is formed on side surfaces of a gate electrodeportion comprising the tunnel insulating film 13, the floating gateelectrode 14, the interelectrode insulating film 15 and the control gateelectrode 16. In the main surface of the substrate 11, n typesource/drain diffusion layers 18 are formed by phosphorous ionimplantation, with the gate electrode portion used as a mask.

An equivalent circuit of the nonvolatile semiconductor memory device ofFIG. 1 is similar to a common EEPROM cell as shown in FIG. 2( a). A NANDcell unit is formed by connecting a plurality of the equivalent circuitsin series, as shown in FIG. 2( b). In FIG. 2( b), M1 to M4 are memorycells, and S1 and S2 are selective transistors.

The basic structure of the present invention described above is the sameas that of a conventional device. In this embodiment, however, thestructure of the tunnel insulating film 13 is different from that of theconventional device. Specifically, as shown in FIG. 3, the tunnelinsulating film 13 of this embodiment has a stacked structure in which asilicon nitride film 13 a is sandwiched by silicon oxide films 13 b and13 c. The silicon nitride film 13 a is obtained by directly nitridingthe silicon substrate 11. By performing the nitriding at hightemperature, the bond state of nitrogen is set to triple coordinate(that is, nitrogen has three bonds to silicon), as shown in FIG. 4.

FIG. 4 illustrates the relationship between the bound energy and thenormalized signal intensity, obtained by XPS (X-ray photoelectronspectroscopy). As shown by a solid line in FIG. 4, a high bound energycomponent, that is, low-density nitrogen bonds decrease by annealing at950° C., and the bond state of nitrogen becomes triple coordination.

In the meantime, in a conventional silicon oxynitride film, a siliconoxide film 23 a is formed by oxidizing a silicon substrate 11 as shownin FIG. 5A, and then nitrogen atoms (N) are injected into the film byexposing the film to, for example, ammonia (NH₃) gas atmosphere as shownin FIG. 5B. The nitrogen injected into the film as described abovecleaves the bonds between silicon and oxygen in the silicon oxide film23 a, and the nitrogen is bonded to the silicon instead of the oxygen.However, it cannot form a triple coordination, but forms doublecoordinate nitrogen bonds. Therefore, as shown in FIG. 5C, the siliconnitride film 23 obtained in the end has double coordinate nitrogenbonds.

The double coordinate nitrogen bonds does not produce any dangling bondsin appearance since each bond of the nitrogen forms a double bond withsilicon. However, this bond is unstable, and easily traps a hole. Thisis caused by formation of level in the vicinity of the valence band ofthe silicon in contact. Specifically, this is because a hole from thesilicon side is trapped by applying a voltage, one bond of each nitrogenforming a double bond with the silicon is cleaved, and a positive fixedcharge is easily formed on the silicon side, and a dangling bond and adefect on the nitrogen side.

In comparison with this, the silicon nitride film 13 a in the tunnelinsulating film 13 according to the embodiment has triple coordinatenitrogen bonds, and thereby nitrogen bonds are stabilized and are noteasily cleaved by electrical stress application.

FIG. 6 is a characteristic diagram comparing a tunnel insulating film ofprior art and that of the present embodiment. In FIG. 6, electric stressis applied to each of the tunnel insulating films, and their leakcurrents (stress-induced leak current: SILC) increased by the stress arecompared. Stress leak current is a leak current which flows throughdefects formed in an insulating film due to electric stress application.The more defects are formed in a film, the more the leak currentincreases.

FIG. 6 shows that the leak current in the tunnel insulating filmaccording to the embodiment hardly increases, although the leak currentin that of prior art monotonously increases with increase in the stressapplication time. Specifically, it shows that the embodiment of thepresent invention suppresses formation of defects in the film, and thatthe tunnel insulating film according to the embodiment is of a highquality. Further, the embodiment has a structure in which a siliconnitride film having triple coordinate bonds each having a stablestructure is located in the central portion of the tunnel insulatingfilm and held between silicon oxide films disposed on and under thereof.This structure can suppress formation of defects in and around thecenter of the film, which most contribute to a stress-induced leakcurrent. Further, although not shown, since a silicon oxide film isformed in the interface on the silicon substrate side, the embodiment isalso effective against well-known deterioration in the interfaceproperty and reliability due to nitrogen introduction.

As described above, the nonvolatile semiconductor memory device of theembodiment has the tunnel insulating film 13 having a three-layerstructure in which the silicon nitride film 13 a having a dielectricconstant twice as large as the silicon oxide films is held between thesilicon oxide films 13 b and 13 c, and the silicon nitride film 13 a hastriple coordinate nitrogen bonds. Therefore, the leak current is reducedeven in a film having the same electric film thickness (oxide-filmconverted film thickness, EOT) as that of prior art. In particular,defect formation due to stress application (that is, in writing anderase with a high electric field) is suppressed, and stress-induced leakcurrent is suppressed.

Further, since the silicon nitride film 13 a has projections anddepressions, the electric field is concentrated in the depressions, andthe embodiment is also effective in reduction in the write voltage.Further, the stacked structure formed of the silicon oxide films 13 band 13 c and the silicon nitride film 13 a suppresses connection ofdefects due to high-voltage stress application from the substrate 11side to the floating gate 14, and suppresses breakdown. Thereby, thelife of the device is prolonged, and the device has a high reliability.Specifically, it is possible to obtain a high-quality and high-reliabletunnel insulating film 13 with reduced defects caused by stressapplication, and improve the reliability of a nonvolatile semiconductormemory device formed of fine elements.

Second Embodiment

FIGS. 7A to 7D are cross-sectional views illustrating steps ofmanufacturing a nonvolatile semiconductor memory device according to asecond embodiment of the present invention.

In this embodiment as shown in FIG. 7A, when a tunnel insulating film(first gate insulating film) is formed, a surface of a silicon substrate11 is directly nitrided by using nitrogen plasma or the like, and asilicon nitride film 13 a having, for example, a 4 nm thickness isformed. Thereafter, as shown in FIG. 7B, a bottom surface and a topsurface of the silicon nitride film 13 a are oxidized by using oxide gasor the like to form silicon oxide films 13 b and 13 c. The presentembodiment is characterized in that the silicon nitride film 13 a isformed to have triple coordination in this step and the surface of thesilicon nitride film 13 a is provided with projections and depressionsas shown in FIG. 7A.

Supposing that the silicon nitride film of triple coordinate is flat,the oxygen gas introduced through the surface or oxygen atoms generatedby the oxygen gas cannot be sufficiently diffused in the triplecoordinate silicon nitride film since the film is stable. Therefore, theoxygen gas or the oxygen atoms cannot reach the interface on the bottomside of the silicon nitride film, and cannot form a silicon oxide filmunder the silicon nitride film. Thus, a thin oxide film is formed onlyon the surface of the silicon nitride film.

In comparison with this, in the second embodiment, since the triplecoordinate silicon nitride film is stable and cohered, it has variancein the film thickness, and serves as the silicon nitride film 13 ahaving projections and depressions as shown in FIG. 7A. Thereby, asshown in FIG. 7B, oxygen molecules or oxygen atoms pass between coheredparts of the silicon nitride film 13 a. Therefore, the surface of thesilicon nitride film is oxidized and the silicon oxide film 13 c isformed, and simultaneously the silicon oxide film 13 b is formed in theinterface on the bottom side of the silicon nitride film. By the abovesteps, the tunnel insulating film 13 is formed as shown in FIG. 7C, andthen a floating gate electrode 14 is formed as shown in FIG. 7D.

Forming a triple coordinate silicon nitride film 13 a which is coheredand has projections and depressions requires nitriding at a hightemperature of 800° C. or more, as shown in FIGS. 8 and 9. FIG. 8illustrates a result of evaluation of silicon nitride film formationtemperature and surface roughness (difference in height betweenprojections and depressions) of a formed silicon nitride film. FIG. 9illustrates the relationship between the silicon nitride film formationtemperature and the bond state.

As shown in FIG. 8, at a low temperature up to 700° C., the increment ofroughness is very small, and the roughness is about 0.07 even at 700° C.Further, at such a low temperature, three-coordinate nitrogen cannot beformed as shown in FIG. 9, and the surface of the nitride film is flat.

The roughness rapidly increases between 700° C. and 800° C., and theroughness at 800° C. exceeds 0.14. At a temperature exceeding 800° C.,the roughness hardly increases, and the roughness at 900° C. is about0.15. Specifically, the roughness is set to 0.14 nm or more by settingthe silicon nitride film formation temperature to a high temperature of800° C. or more, and it is possible to form a triple coordinate siliconnitride film 13 a having a desired roughness.

The pressure in nitriding also has an influence on the roughness. Evenat high temperature, if nitriding is performed at low pressure, a flattriple coordinate silicon nitride film 13 f is formed as shown in FIG.8.

FIG. 10 is a characteristic diagram illustrating the film formationtemperature and the film formation pressure in formation of the siliconnitride film, and the influence of the temperature and pressure on thefilm quality. At a film formation temperature less than 600° C., atriple coordinate silicon nitride film cannot be formed, and a doublecoordinate silicon nitride film 23 is formed as shown by A of FIG. 10.Although nitriding at a high temperature of 600° C. or more enablesformation of a triple coordinate silicon nitride film, a flat film 13 fis formed as shown by B of FIG. 10 with a film formation temperature ofless than 800° C. Even with a film formation temperature of 800° C. ormore, if the pressure is less than 10 Torr (1330 Pa), a flat film 13 fis formed.

In comparison with this, in the embodiment, nitriding is performed at atemperature of at least 800° C. and a film formation pressure of atleast 10 Torr (1330 Pa), and thereby a cohered silicon nitride film 13 ahaving projections and depressions is formed, as shown by C of FIG. 10.This is because the high pressure increases the amount of nitrogen whichreach the surface of the silicon substrate, and promotes nitriding.

In consideration of the above, in the process of forming the tunnelinsulating film used in the second embodiment, it is required to performformation of a silicon nitride film of the tunnel insulating film at ahigh temperature of at least 800° C. and under a pressure of at least 10Torr (13 Pa).

FIG. 11 illustrates a profile of oxygen concentration in a tunnelinsulating film formed by oxidizing the above triple coordinate siliconnitride film having projections and depressions. A silicon nitride filmformed of triple coordinate nitrogen is not easily oxidized byintroduction of oxygen. Therefore, in a flat silicon nitride film 13 fas shown by A of FIG. 11, oxygen cannot reach the interface between thesilicon substrate and the silicon nitride film as described above.

In the meantime, in a silicon nitride film 23 having unstable doublecoordinate nitrogen bond, oxygen easily enters the silicon nitride filmas shown by C of FIG. 11. Therefore, even in a flat film, the siliconnitride film is also broken simultaneously with arrival of oxygen at theinterface between the silicon substrate and the silicon nitride film,and an oxynitride film is formed. This film easily generates defectswhen a high electric-field stress is applied.

In comparison with this, if the silicon nitride film 13 a formed ofcohered triple coordinate nitrogen bond according to the secondembodiment is used as shown by B of FIG. 11, the structure of thesilicon nitride film 13 a is not easily broken by oxygen introductionsince it has triple coordination. Further, oxygen is introduced throughthe depressions of the cohered silicon nitride film 13 a, and therebythe silicon oxide film 13 b is formed in the interface between thesilicon substrate and the silicon nitride film. Consequently, a tunnelinsulating film 13 is formed, comprising the silicon nitride film 13 aheld between the silicon oxide films 13 b and 13 c, as shown in FIG. 2.

FIG. 12 is a characteristic diagram of MOS structures comprising acontinuous silicon nitride film, or a discontinuous silicon nitridefilm, held between silicon oxide films. The horizontal axis indicatesgate voltage, and the vertical axis indicates capacity value defined bya capacity (Cox) when a voltage of 4 MV/cm is applied to the insulatingfilm. The structure comprising a continuous or discontinuous film heldbetween silicon oxide films is publicly known as MONOS memory or dotmemory. In these publicly-known examples, the silicon nitride filmitself is used as a place to trap charges to obtain memory property.

As an example, the embodiment A is compared with a dot silicon nitridefilm (particulate silicon nitride film 13 g) B. Since a MONOS memory anddot memory utilizes trap formation of a silicon nitride film, thesilicon nitride film to be used includes double coordinate nitrogen.Thereby, charges are trapped in the silicon nitride film by applying ahigh electric field, and the voltage/capacity characteristic thereofshifts in correlation with the polarity and quantity of the trappedcharges. The Example of B in FIG. 12 illustrates the case whereelectrons are trapped by the silicon nitride film dots 13 g.

In comparison with this, in the second embodiment, since the tunnelinsulating film 13 comprises the silicon nitride film 13 a includingtriple coordinate nitrogen bond which suppresses trap generation, as inthe example A of FIG. 12, the voltage/capacity characteristic does notshift after application of high-electric-field stress.

Third Embodiment

FIGS. 13A to 13I are cross-sectional views illustrating steps ofmanufacturing a nonvolatile semiconductor memory device according to athird embodiment of the present invention. The same constituent elementsas those in FIG. 1 are denoted by the same respective referencenumerals, and detailed explanation thereof is omitted.

First, as shown in FIG. 13A, prepared is a p type silicon substrate 11having, for example, a surface orientation of (100) and a resistivity of10 to 20 Ωcm. Grooves are formed in the surface of the p type siliconsubstrate 11, and CVD oxide films are embedded therein. Thereby, deviceisolation insulating films 12 each having an about 0.6 μm thickness areformed.

Next, as shown in FIG. 13B, a silicon nitride film 13 a having a 4 nmthickness is formed on the main surface of the substrate 11 by usingplasma nitriding, at a temperature of 900° C. and a pressure of 50 Torr(6550 Pa). Then, as shown in FIG. 13C, the silicon nitride film 13 a isexposed to an oxygen gas atmosphere to introduce oxygen atoms. Thereby,as shown in FIG. 13D, formed is a tunnel insulating film (first gateinsulating film) 13 comprising the silicon nitride film 13 a heldbetween silicon nitride films 13 b and 13 c. Thereafter, as shown inFIG. 13E, a phosphorus-doped n-type polycrystalline silicon film with a200 nm thickness is deposited as a floating gate electrode 14 on thetunnel insulating film 13.

Next, as shown in FIG. 13F, an ONO film 15 having a 7 nm thickness, forexample, is formed as an interelectrode insulating film (second gateinsulating film) on the polycrystalline silicon film serving as thefloating gate electrode 14. Then, as shown in FIG. 13G, aphosphorus-doped n-type polycrystalline silicon film having a 200 nmthickness is deposited as a control gate electrode 16 on the ONO film15.

Next, as shown in FIG. 13H, a resist mask 21 is formed, and thereafterthe polycrystalline silicon film 16, 14, the tunnel insulating film 13and the ONO film 15 are etched by reactive ion etching to form a gateportion. Then, after the resist mask 21 is removed, the structure issubjected to heat treatment in an oxidizing atmosphere for the purposeof recovery from processing damage, and an after oxide film 17 of about3 nm is formed. Parts of the silicon oxide film 17 on the control gateelectrode 16 and on the source/drain regions are removed for wireformation described below.

Next, for example, 3×10¹⁵ cm⁻² of phosphorous ions are injected into thewhole surface, and the structure is subjected to heat treatment at 1000°C. for 20 seconds to diffuse and activate the phosphorus in the siliconsubstrate 11. Thereby, diffusion layers 18 serving as source/drainregions are formed. By the above steps, the structure shown in FIG. 13Iis obtained.

The steps following the above are not specifically illustrated. Forexample, a silicon oxide film of a 300 nm thickness is deposited on thewhole surface by CVD, and then a contact hole is provided in the siliconoxide film by anisotropic dry etching. Thereafter, an aluminum filmhaving a 800 nm thickness and containing, for example, 0.5% of siliconand 0.5% of copper is formed, and an electrode is formed by patterningthe aluminum film. Then, the structure is subjected to heat treatment ina nitrogen atmosphere containing 10% of hydrogen, at 450° C. for 15minutes.

As described above, according to the third embodiment, the siliconnitride film which forms the tunnel insulating film 13 includes triplecoordinate bonds, and thereby it is possible to form a nonvolatilesemiconductor memory device having a high-quality and high-reliabletunnel insulating film 13. Further, by setting the thickness of thesilicon nitride film forming the tunnel insulating film 13 to 4 nm andeach of the silicon oxide films to 2 nm, the physical thickness of thetunnel insulating film 13 is 8 nm, and the oxide film convertedthickness (EOT) is 6 nm. Specifically, the tunnel insulating film itselfis thinned. This contributes to reduction in the power supply voltage,and enables improvement not only in the property but also in thereliability of the device.

Although direct nitriding using nitrogen plasma is explained as anexample of the method of forming a silicon nitride film including triplecoordinate nitrogen bonds, the present invention is not limited to it.For example, the same effect is obtained by nitriding using ammonia(NH₃) gas or nitrogen radicals. In the case of using ammonia gas,hydrogen is introduced into the silicon nitride film. Therefore, thehydrogen in the film may be removed by heat treatment in a vacuum or innitrogen or inert gas at a temperature higher than the silicon nitridefilm formation temperature, after the silicon nitride film is formed.

If heat treatment is performed in a vacuum or in nitrogen or inert gasat a temperature higher than the nitriding temperature after the siliconnitride film is formed, relaxation of the structure of the siliconnitride film is promoted, and it is possible to obtain a triplecoordinate silicon nitride film having a more stable structure. Thisholds true not only for the case of forming a silicon nitride film byammonia gas, but also for the case of forming a silicon nitride film byother methods.

Further, although oxidation using oxygen (O₂) gas is explained as anexample of the oxidation (FIG. 13C) after formation of the siliconnitride film, the present invention is not limited to it. For example,the same effect is obtained by oxidation using ozone (O₃) gas, gascontaining water vapor (H₂O), oxygen radicals, or dinitrogen monoxide(N₂O) gas. However, if nitric oxide (NO) gas is used for the oxidation,nitrogen is introduced into the silicon oxide film formed in theinterface between the silicon nitride film and the silicon substrate.The nitrogen easily forms double coordinate nitrogen bond, thus maycause deterioration in the interface property and increase in traps.

Therefore, it is not desirable to use NO gas. Further, the oxidation ispreferably performed at 900° C. or more, to improve the quality of thesilicon oxide films to be formed.

Fourth Embodiment

FIGS. 14A to 14D are cross-sectional views illustrating steps ofmanufacturing a nonvolatile semiconductor memory device according to afourth embodiment of the present invention. The same constituentelements as those in FIG. 1 are denoted by the same respective referencenumerals, and detailed explanation thereof is omitted.

The steps up to formation of a polycrystalline silicon film serving as afloating gate electrode 14 are the same as the steps shown in FIGS. 13Ato 13E.

Next, as shown in FIG. 14A, an aluminum oxide film 25 having a 15 nmthickness or the like is deposited as an interelectrode insulating film(second gate insulating film) by CVD on the polycrystalline silicon filmserving as the floating gate electrode 14. Next, as shown in FIG. 14B, aphosphorus-doped n-type polycrystalline silicon film having a 200 nmthickness is deposited as a control gate electrode 16 on the aluminumoxide film 25.

Next, as shown in FIG. 14C, a resist mask 21 is formed, and thereafterthe polycrystalline silicon film 16 and 14, the tunnel insulating film13 and the aluminum oxide film 25 are etched by reactive ion etching toform a gate electrode portion. Then, after the resist mask 21 isremoved, the structure is subjected to heat treatment in an oxidizingatmosphere for the purpose of recovery from processing damage, and anafter oxide film 17 of about 3 nm is formed.

Next, for example, 3×10¹⁵ cm⁻² of phosphorous ions are injected into thewhole surface, and the structure is subjected to heat treatment at 1000°C. for 20 seconds to diffuse and activate the phosphorus in the siliconsubstrate 11. Thereby, diffusion layers 18 serving as source/drainregions are formed. By the above steps, the structure shown in FIG. 14Dis obtained.

The steps following the above are not specifically illustrated. In thesame manner as in the third embodiment, a silicon oxide film isdeposited by CVD, and then a contact hole is provided in the siliconoxide film. Thereafter, an aluminum film is formed, and an electrode isformed by patterning the aluminum film. Then, the structure is subjectedto heat treatment in a nitrogen atmosphere.

According to the fourth embodiment, the insulating film between thefloating gate electrode 14 and the control gate electrode 16 is formedof the aluminum oxide film 25 being a high dielectric film. Therefore,it is possible to increase the coupling ratio with the tunnel insulatingfilm 13. It is thus possible to make a gate electrode portion having asimple plane stacked structure, and solve the problem of interferencebetween cells due to scale down of the device.

If a high dielectric film 25 formed of metal oxide or the like isprovided between the floating gate electrode 14 and the control gateelectrode 16, metal impurities 22 are diffused through particleboundaries in the polycrystalline silicon film of the floating gateelectrode 14, and introduced into the tunnel insulating film 13 as shownin FIG. 15. In conventional tunnel insulating films, since the metalimpurities 22 are easily introduced into the film, traps are formed andthe resistance to pressure is greatly deteriorated.

In comparison with this, in the case of using the tunnel insulating film13 of the fourth embodiment, the silicon nitride film 13 a having astable structure prevents diffusion of the metal impurities 22.Simultaneously, a stacked structure of the tunnel insulating film 13including the silicon oxide films 13 b and 13 c and the silicon nitridefilm 13 a prevents defects formed in stress application due to the metalimpurities from being connected from the floating gate electrode 14 andthe silicon substrate interface. Therefore, it is also possible tosuppress deterioration in the resistance to breakdown.

In the above embodiment, although an aluminum oxide (Al₂O₃) film isadopted as an example of the high-dielectric film 25 located between thefloating gate electrode 14 and the control gate electrode 16, thepresent invention is not limited to it. For example, the same effect isobtained by using a metal oxide having a high dielectric constant, analuminate film (MA₁O_(X), M: metal element, x: oxygen content), asilicate film (MsiO_(X), M: metal element, x: oxygen content), an oxideof transition element such as HfO₂, ZrO₂ and CeO₂, and metal oxide suchas Ln₂O₃. Further, if the interelectrode dielectric film is formed of astacked layer of aluminum oxide and hafnium oxide, defects such asoxygen deficit in the aluminum oxide film are resolved with atomicoxygen at low temperature, and thereby a structure with a reduced leakcurrent is obtained.

Fifth Embodiment

FIG. 16 is a cross-sectional view illustrating a schematic structure ofa nonvolatile semiconductor memory device according to a fifthembodiment of the present invention.

In the fifth embodiment, silicon oxide films 12 for device isolation areformed on a p type silicon substrate 11. In the surface of the siliconsubstrate 11, n-type source/drain diffusion layers 18 are formed byphosphorus ion implantation. A tunnel insulating film (first gateinsulating film) 13 having a stacked structure formed of a siliconnitride film 13 a held between silicon oxide films 13 b and 13 c isformed on the surface of the silicon substrate 11. A polycrystallinesilicon film serving as a floating gate electrode 14 is formed on thetunnel insulating film 13.

On the floating gate electrode 14, formed is an interelectrodeinsulating film 35 serving as a second gate insulating film. Theinterelectrode insulating film 35 has a stacked structure formed of asilicon nitride film 35 a held between silicon oxide films 35 b and 35c. A polycrystalline silicon film serving as a control gate electrode 16is formed on the interelectrode insulating film 35. Further, a siliconoxide film 17 is formed on side walls of the gate electrodes 14 and 16.

Specifically, the interelectrode insulating film has the structure inwhich the silicon nitride film 35 a is held between the silicon oxidefilms 35 b and 35 c, in the same manner as the tunnel insulating film13. The other parts of the memory device are the same as those in thestructure of the device in FIG. 1. The silicon nitride film 35 a isobtained by directly nitriding the floating gate electrode 14. Byperforming the nitriding at high temperature, nitrogen includes triplecoordinate bonds.

According to the above structure, the interelectrode insulating film 35held between the floating gate electrode 14 and the control gateelectrode 16 also has the insulating film structure as shown in FIG. 3.This structure further improves the reliability of the device, andsimultaneously reduces the drive voltage of the device.

Sixth Embodiment

FIGS. 17A to 17D are cross-sectional views illustrating steps ofmanufacturing a nonvolatile semiconductor memory device according to asixth embodiment of the present invention. The same constituent elementsas those in FIG. 1 are denoted by the same respective referencenumerals, and detailed explanation thereof is omitted.

Steps up to formation of a polysilicon film serving as a floating gateelectrode 14 are the same as the steps shown in FIGS. 13A to 13E.

Next, as shown in FIG. 17A, a silicon nitride film 35 a having a 4 nmthickness is formed on the polycrystalline silicon film serving as thefloating gate electrode 14, by using plasma nitriding or the like at a900° C. temperature and a pressure of 50 Torr (6550 Pa). Then, thesilicon nitride film 35 a is exposed to, for example, an oxygen gasatmosphere to introduce oxygen atoms into the film. Thereby, as shown inFIG. 17B, formed is an interelectrode insulating film (second gateinsulating film) 35 formed of the silicon nitride film 35 a held betweensilicon oxide films 35 b and 35 c.

Next, as shown in FIG. 17C, a phosphorus-doped n-type polycrystallinesilicon film having a 200 nm thickness is deposited as a control gateelectrode 16 on the interelectrode insulating film 35.

Next, although not shown in the embodiment, patterning is performed witha resist mask used, and thereafter the polycrystalline silicon films 16and 14, the tunnel insulating film 13 and the interlayer insulating film35 are etched by reactive ion etching to form a gate electrode portion.Then, after the resist mask is removed, the structure is subjected toheat treatment in an oxidizing atmosphere for the purpose of recoveryfrom processing damage, and an after oxide film 17 of about 3 nm isformed.

Next, for example, 3×10¹⁵ cm⁻² of phosphorous ions are injected into thewhole surface, and the structure is subjected to heat treatment at 1000°C. for 20 seconds to diffuse and activate the phosphorus in the siliconsubstrate 11. Thereby, diffusion layers 18 serving as source/drainregions are formed. By the above steps, the structure shown in FIG. 17Dis obtained.

The steps following the above are not specifically illustrated. In thesame manner as in the third embodiment, a silicon oxide film isdeposited by CVD, and then a contact hole is provided in the siliconoxide film. Thereafter, an aluminum film is formed, and then anelectrode is formed by patterning the aluminum film. Then, the structureis subjected to heat treatment in a nitrogen atmosphere.

Direct nitriding using nitrogen plasma has been explained as an exampleof the method of forming a silicon nitride film including triplecoordinate nitrogen bonds, in the step of forming the interelectrodeinsulating film 35 held between the floating gate electrode 14 and thecontrol gate electrode 16. However, the embodiment is not limited to it,but various modifications are possible as explained in the thirdembodiment.

Further, oxidation using oxygen (O₂) gas has been explained as anexample of the oxidation performed after formation of the siliconnitride film. However, the embodiment is not limited to it, but variousmodifications are possible as explained in the third embodiment.Further, the oxidation is preferably performed at 900° C. or more, toimprove the quality of the silicon oxide films to be formed.

Seventh Embodiment

FIGS. 18A to 18E are cross-sectional views illustrating steps ofmanufacturing a nonvolatile semiconductor memory device according to aseventh embodiment of the present invention. The same constituentelements as those in FIG. 1 are denoted by the same respective referencenumerals, and detailed explanation thereof is omitted.

In FIGS. 7A to 7D, the structure is exposed to an oxidizing gas such asoxygen after formation of the silicon nitride film, and thereby thesilicon oxide films are formed to hold the silicon nitride filmtherebetween. However, since the silicon nitride film has triplecoordinate bond, the surface of the silicon nitride film has slowoxidation speed.

To solve this problem, in the seventh embodiment, after a siliconnitride film 13 a is formed as shown in FIG. 18A, a silicon film 13 ddeposited thereon as shown in FIG. 18B. Thereafter, as shown in FIG.18C, the structure is exposed to an oxidizing gas such as oxygen, andthereby the silicon oxide film 13 d is oxidized and a silicon oxide film13 c is formed. Simultaneously, oxidant passes through the siliconnitride film 13 a, and a silicon oxide film 13 b is formed in a regionheld between the substrate 11 and the silicon nitride film 13 a.Thereby, formed is a tunnel insulating film (first gate insulating film)13 having a structure in which the silicon nitride film 13 a is heldbetween the silicon oxide films 13 b and 13 c. Thereafter, apolycrystalline silicon film is deposited thereon to form a floatinggate electrode 14.

By adopting the above process, it is possible to control the thicknessof the silicon oxide film 13 c on the silicon nitride film 13 a by thethickness of the silicon film 13 d to be deposited. The silicon film 13d formed on the silicon nitride film 13 a may be any of an amorphoussilicon film, a polycrystalline silicon film and a monocrystallinesilicon film. It is desirably an amorphous silicon film for uniformdeposition on the surface of the silicon nitride film.

Although the silicon film 13 d may be a polycrystalline silicon film,the silicon crystal particles thereof have different surfaceorientations. Therefore, if the oxidation amount is insufficient, thereare cases where silicon particles 24 remain in the silicon oxide film 13c, as shown in FIG. 19. Although it is basically undesirable that thesilicon particles 24 remain, it is possible to positively use thephenomenon and form a semiconductor memory device utilizing the effectsof the particles, such as storing charges in the silicon particles 24.

Further, if the silicon film is deposited at a high temperature of 700°C. by using, for example, a silane (SiH₄) gas and dichlorsilane(SiH₂Cl₂) gas, the deposited silicon film is a monocrystalline siliconfilm. Since a monocrystalline silicon film is uniformly oxidized, it ispossible to form a silicon oxide film 13 c with a higher quality.

Modification

The present invention is not limited to the above embodiments. Althoughsilicon is used as the substrate in the embodiments, it is possible touse a substrate of other semiconductors. Further, if a single-layer filmis used as the second gate insulating film, an insulator having adielectric constant higher than that of the silicon oxide films ispreferably used, to heighten the coupling ratio with the control gateelectrode and the floating gate electrode. For example, it is desirableto use a metal oxide, a metal silicate film, or a metal aluminate filmas the insulator.

Further, the method of forming a silicon nitride film on the substratein formation of the first gate insulating film is not necessarilylimited to plasma nitriding. Any method can be adopted as long as it isa method of forming a silicon nitride film by directly nitriding thesubstrate. Although the nitriding temperature and the nitriding pressurecan be changed according to necessity, they are preferably set to atemperature of at least 800° C., and a pressure of at least 1330 Pa, toobtain triple coordinate nitrogen bonds and provide projections anddepressions to the surfaces of the film. Further, the temperature information of oxide films after the silicon nitride film is formed ispreferably 900° C. or more to obtain silicon oxide films of highquality.

Furthermore, the material of the floating gate electrode and the controlgate electrode are not necessarily limited to polycrystalline silicon,but it is possible to use other conductive materials. However, if thesecond gate insulating film is structured in the same manner as thefirst gate insulating film as in the fifth and sixth embodiments, it isrequired that the floating gate electrode is formed of silicon.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcept as defined by the appended claims and their equivalents.

1. A method of manufacturing a nonvolatile semiconductor memory device,comprising: forming a tunnel insulating film by directly nitriding amain surface of a silicon layer of a first conductivity type by heatingthe silicon layer to 800° C. or more and setting an atmosphere pressureof 1330 Pa or more to form a silicon nitride film, heating the siliconlayer in an oxidizing atmosphere, to form first silicon oxide films, onein an interface between the silicon nitride film and the silicon layerand the other on the silicon nitride film, and forming a control gateelectrode above the tunnel insulating film.
 2. A method according toclaim 1, wherein forming the silicon nitride film includes directlynitriding the main surface of the silicon layer by plasma nitriding. 3.A method according to claim 1, wherein forming the silicon nitride filmincludes setting a temperature at which the silicon layer is heated whenthe silicon nitride film is oxidized to 900° C. or more.
 4. A methodaccording to claim 1, further comprising: forming a floating gateelectrode on the tunnel insulating film; and forming an interelectrodeinsulating film on the floating gate electrode; wherein the control gateelectrode is formed on the interelectrode insulating film.
 5. A methodof manufacturing a nonvolatile semiconductor memory device, comprising:forming a tunnel insulating film by directly nitriding a main surface ofa silicon layer of a first conductivity type by heating the siliconlayer to 800° C. or more and setting an atmosphere pressure of 1330 Paor more to form a silicon nitride film, forming a silicon film on thesilicon nitride film and then heating the silicon layer in an oxidizingatmosphere to oxidize the silicon film and form a first silicon oxidefilm, and to form a second silicon oxide film in an interface betweenthe silicon nitride film and the silicon layer, and forming a controlgate electrode above the tunnel insulating film.
 6. A method accordingto claim 5, wherein forming the silicon nitride film includes directlynitriding the main surface of the silicon layer by plasma nitriding. 7.A method according to claim 5, wherein forming the silicon nitride filmincludes setting a temperature at which the silicon layer is heated whenthe silicon nitride film is oxidized to 900° C. or more.
 8. A methodaccording to claim 1, wherein the silicon nitride film in the tunnelinsulating film has projections and depressions on its surfaces and iscontinuously formed in an in-plane direction.
 9. A method according toclaim 8, wherein an average of differences between the projections anddepressions is set at 0.14 nm or more.
 10. A method according to claim1, wherein an upper surface of an upper one of the silicon oxide filmsare more planar than the silicon nitride film.
 11. A method according toclaim 4, wherein to form the interelectrode insulating film, forming asecond silicon nitride film by directly nitriding a surface of thefloating gate electrode, followed by heating the silicon layer in anoxidizing atmosphere, to form second silicon oxide films, one in aninterface between the second silicon nitride film and the floating gateelectrode and the other on the second silicon nitride film.
 12. A methodaccording to claim 5, wherein the silicon nitride film in the tunnelinsulating film has projections and depressions on its surfaces and iscontinuously formed in an in-plane direction.
 13. A method according toclaim 12, wherein an average of differences between the projections anddepressions is set at 0.14 nm or more.
 14. A method according to claim5, wherein an upper surface of an upper one of the silicon oxide filmsare more planar than the silicon nitride film.
 15. A method according toclaim 5, further comprising: forming a floating gate electrode on thetunnel insulating film; and forming an interelectrode insulating film onthe floating gate electrode; wherein the control gate electrode isformed on the interelectrode insulating film.